The antioxidant activities (AoAs) of 50 different technical lignins have been determined. The lignins of various botanical origins (annual plants, coniferous trees, and deciduous trees) were isolated and fractionated by different techniques (delignification by alkali, kraft process, fast pyrolysis, and hydrolysis). The structure and the functionality of lignins were characterized by functional group analyses (phenolic OH, carboxyl, and methoxyl groups), analytical pyrolysis pyrolysis/gas chromatography/mass spectrometry/flame ionization detector (Py-GC/MS/FID), electron paramagnetic resonance, size exclusion chromatography, and titrimetric methods, and the AoAs were evaluated as the capacity to scavenge the DPPH· and ABTS·+ free radicals. The relationship between the lignin structure and the AoA was characterized by pair correlation, partial correlation, and multivariate regression analyses, including correlated components regression. The results were compared with those of lignin model compounds and low molecular weight phenylpropanoids. It has been shown that molecular weight does not influence essentially the AoA of lignins. There is a relationship between the activities of low and high molecular weight polyphenols; their mechanisms of action are also similar. The structure-related AoA of lignins has been quantified for the first time.
A fraction of pyrolytic oils (PyO) – obtained by fast pyrolysis of alder (Alnus incana), ash-tree (Fraxinus excelsior) and aspen (Populus tremula) in a laboratory scale reactor – was precipitated in water. This hydrophobic moiety of PyO is called pyrolytic lignin (PyL). The composition of the volatile monomeric compounds of PyO and the PyL fraction was determined by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). It has been found that PyL has a high content of phenolic products (between 75% and 83%), which varies depending on the wood species. The antioxidant properties of the PyL fraction were studied and it was demonstrated that the antioxidant activity determined in different tests exceeded the corresponding activity of alkali lignin. The antioxidant properties of PyL are on the same level as those of the widely used antioxidants, such as rutin, trolox, curcumine, and tert-butylhydroquinone (TBHQ). A new method was developed for the extraction of a monomeric phenol fraction (Py-monPh) from PyO by means of the organic solvent methyl tert-butyl ether (MTBE). The Py-monPh can be considered as a promising source of antioxidants.
The bark of trees has a big potential as a source of green chemicals. The aim of the present work was to valorise the potential of deciduous tree species with this regard. Three widely spread trees in Europe (grey alder, ash tree, aspen) were in focus as a source of polyphenols, and the yields of polyphenolic compound in the extracts were considered as evaluation criteria. The highest yields of hydrophilic extractives were found in barks of grey alder and aspen (36.8 and 22.9%, respectively). In the former, the highest antioxidant activity was found towards free radicals (DPPH• and ABTS•+) and superoxide anion radical. Open chain diarylheptanoids, mainly oregonin, were identified as the major constituents of the grey alder hydrophilic extract. In addition to oregonin, the presence of 2 linear diarylheptanoids [platyphylloside and 1,7-bis-(3,4-dihydroxyphenyl)-heptane-5-O-β-D-glucopyranoside] was confirmed. For the first time, the compounds 1,7-bis-(3,4-dihydroxyphenyl)-3-hydroxyheptane-5-O-β-D-xylopyranoside and 1,7-bis-(3,4-dihydroxyphenyl)-heptane-3-one-5-O-β-D-glucopyranoside were detected in grey alder bark. The results of experiments in vitro and in vivo have shown the high potential for diarylheptanoids-containing extracts in prophylaxis and/or treatment of diseases due to the metabolic disorders and ageing. The biological activity of grey alder extract was confirmed in in vitro experiments by incubation of human blood samples. In vivo experiments with rats also showed positive results. The conclusion is that grey alder extracts have a high potential for prevention of ageing related pathologies. Besides diarylheptanoids, the bark contains condensed tannins in commercially available quantity (12.5%). Eco-friendly wood adhesives were obtained on a tannins basis. The bark left after polyphenols isolation can be used in soil melioration and as a sorbent for the removal of oil products from water surface. The investigation of the phenolic pool of grey alder could contribute to cluster technologies within the biorefinery-based bark processing.